Polymerization products and processes for producing the same



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This invention relates to themanufacture of new and useful products.,generally of high molecular weight, or poleric in nature, by causingsulfur dioxide to react with unsaturated ccmpounds other than the` oleor conjugated diolen hydrocarbons, and to processes by which suchreacticnscan be made to take place.

A further object of the invention is to produce high molecular weichtcompounds containing sulfur dioxide and having incorporated in themolecule, radicals such as the hydroxyl or carbonyl, capable ofundergoing further reaction with suitable chemical agents.

Other objects will appear as theA invention is more fully described.

Prior literature references to the reactions of SO2 with unsaturatedcompounds are conned to the olefin and diolen hydrocarbons. Mathews andElder, Brit. 11,635, 1914, claim the reaction of liquid SO2 with olechydrocarbons, such as ethylene, propylene, and butylenes in sunlight orultraviolet light. De Bruin, Chem. Abs. 9,623 (1915) found that theconjugated diene, isoprene, when allowed to stand with liquid SO2. formsa crystalline compound. Mathews and Strange, U. S. 1,196,259 (1916),react isoprene and other conjugated dioleins with Si): in the presenceofv halogen compounds such as HCl, iodine or acetyl chloride, whichpro/mote the formation lof the crystallizable sulfoxide. BadischeAniline and Sodafabrik, Ger. 236.3% (lull) Staudinger, G-er. 506,839(1930) and Fermes, Can.' 329,043, (1933) disclose-the reaction oi' 80swith oleilr'is having conjugated double bonds. Ieopold Singer in FrenchPat. 515,59@ (iuulidiscloses a process for conjugated diolenhydrocarbons react with SO2 to. form lush molecular weight polymers of aresinous nature.

We have reacted the following materials with sulfur dioxide: Y

The unsaturated 'halogen derivatives, vinyl chloride and allyl chloridereact readily with lici-a uid S02 in the presence oi a cat or in light.

Application January Serial No. W852i (El. 26d-2) 'heat and pressure.

The vinyl chloride forms a white solid which is insoluble in S02, butwhich can be molded by The allyl .chloride forms a water white, classyproduct somewhat soluble in SO2. After molding by heat and pressure, theresin exhibits high mechanical strength. The unsaturated alcohol, allylalcohol, reacts readily with 80a in the presence of catalyst or light.The solid resin obtained has a. very high tensile strength.

The unsaturated ether, allyl ethyl ether, reacts readily with. sol m thepresence or catalyst or light. The solid resinous product can be moldedby heat and pressure.

The olefin oxides, or innerethers, ethylene oxide and propylene oxidereact relatively more slowly'with SO: in the presence of catalyst orlight at temperatures hup to 40 C. but preferably at about C. Theproducts are viscous fluids useful as softening agents.

forming a compound of high molecular weight.

Diallyl, a diolen not having conjugated double bonds and consequentlynot 'being capable of undergoing 1 4 addition of SO2, was found to reactrapidly with S02 to form ya white insoluble dimcultly fusible solid. e

\ The unsaturated aldehyde, acrolein, reacts slowly with 80a in thepresence of light or catalyst. The reaction can best be carried out attemperatures below atmospheric. The product is a solid insoluble in $62.

The unsaturated acids, acrylic, allylacetic, and undecylenic reactreadily with SO2 in the presence ci a catalyst or light.' The productsare insoluble in the excess Soi.l 'I hey are softer than the productsobtained from oleiinic hydrocarbons of the same number of carbon atoms,the product of undecylenic acid being very soft and pliable.

The acetylene derivatives, ethyl acetylene and phenyl acetylene, reactwith SO2 in the presence of light or a catalyst.

The acetylene polymers. vinyl acetylene, di-

l vinyl acetylene, and poly-divinylacetylene. react slowly in liquid BO:in the lig-ht or in the pres'- are: crctonyl alcolici, chloroprenenbromoprene..

unsaturated vegetable oils such as tung oil, and

partiallychlorinated olenns such as the cilchlo-4 ride of diallyl.

in most cases Wehave found that the treatment ci the unsaturated productto remove any absorbed oxygen and oxidation products .prior to reactionis desirable. f

Although the reaction involves approximately equimolecular proportionsof SO2 and unsaturated compound the reaction product usually In manyways the production of resins from such compounds as unsaturated halogenderivatives, alcohols, .ethers, esters, acids and aldehydes, ormaterials contaminar them. by reaction with S02 is'highly desirable andadvantageous. It would permit the production of resins having specialproperties; for example the allyl .alcohol-S02 resin has unusually hightensile strength. while the undecylenic acid-SO2 and ethyl ac-j'rylate-SOz resins are soft and rubbery. Then, too, a resin in which istied up such a compound of multiple. functions should be capable offurther modiiication of properties hy other chemical reactionsaiterformation of the SO2 complex. .Apparently only the carbon to carbondouble bond is involved in the resin reaction, leaving the otherlfunctional groups, such as hydroxyl or carhoxyL'more or less free toundergo its characteristic reactions. Thus, an allyl alcohol resin or anacrylic acid resin might be esterified in the usual manner with acidanhydrides or alcohols, respectively, to produce resins with a widerange of properties. Still another advantage of the use of thesecompounds is that they can he used to modify the properties of resinsfrom unsaturated hydrocarbons and i :f alcohol7 reacts y tutorat@ rie.,vhlm@ brwm.

'.lhis he accomplied in either ci tw ways; the unsat-a uratedpolyiunctlonal compound may be mixed with the unsaturated hydrocarbonand SO2 leeiiore reaction; in which case opportunity is aftforded formolecules oi both types of unsaturated compounds to build into the sameresin molecule;

or the resins of the two types of compounds may he formed by reactingseparately with S02, and then be blended in the desired proportionsafter reaction. I

We have produced useful resinous products by the reaction of S02 withunsaturated compounds other than simple olehnic hydrocarbons andconiugated diolenic hydrocarbons, have blended the resins so obtainedwith resins formed by the :reaction of SO2 with simple oleins and/or diolefins in order tomodiiy the properties of` the latter and have alsomixed such unsaturated compounds with the simple oleins and diolens andreacted the mixture with S02 under the proper conditions. The followingexamples will illustrate the process oi the present invention:

2i. Equal volumes of liquid S02 and allyl chloride are sealed in a glasstube and exposed to sunlight or artificial light, preferably of shortwave length. After tire reaction has gone to completion, as indicated hythe conversion ofthe uid reactants to a stiff gel,.the excess S02 isallowed to evaporate, leaving a white solid resin.

As a variation of the above, suitable for larger scale operation, themixture of SO2 and allyl chloride is placed in a bomb or autoclaveprovided with a suitable source ofv internal illumination and thereaction is promoted photochemically.

II. Equal volumes oi' liquid S02 and allyl alcohol are placed in a bombor autoclave containing 0.01-0.l per cent of silver nitrate, or othersuitable catalyst and. are allowed to react after thorough mixing. Afterthe reaction has gone to completion, the excess SO2 is allowed to escapeand the solid resin is removed from the vessel.

Having described our invention, what we claim is:

l. The process oi' producing high molecular weight polymeric productswhich comprises reracting sulfur dioxide with unsaturated compoundsselected irom the group; vinyl chloride and allyl chloride.

2. e process of producing high molecular weight polymeric products whichcomprises reacting sulfur dioxide with vinyl chloride.

3. The process of producing high molecular .weight polymeric productswhich comprises reacting sulfur diomde with allyl chloride. FRlmERICK E.FREE.

HENRY FITCH, JR. ROBERT DEWEY SNOW.

